Plasticized halogen-containing resins



States Patent 3,149,087 PLASTICIZED HALOGEN-CONTAINING RESINSConstantine E. Anaguostopoulos, Kirkwood, and Albert J. Lauck, WebsterGroves, Mo., assignors to Monsanto Company, a corporation of Delaware NoDrawing. Filed Nov. 8, 1961, Ser. No. 150,894 30 Claims. (Cl. 260-31.6)

This invention relates to new and useful compositions comprisinghalogen-containing vinyl resins and relates more particularly tocompositions comprising halogencontaining vinyl resins plasticized withlow molecular weight, terminated, unsaturated polyesters. The inventionhas special utility for the production of halogen-containing vinyl resinplastisols, organosols and dry blends wherein said polyesters functioneifectively as polymerizable plasticizers which significantly improvecertain physical properties of the starting resin.

Halogen-containing vinyl resins such as polyvinyl chloride and itscopolymers, which are widely employed in the plastics industry, aregenerally hard and brittle in their unplasticized state. Althoughunplasticized polyvinyl chloride has an indefinite flexibility point ofapproximately 75 to 80 C., the unplasticized resins do not become fused,fluid, pliable, mobile or workable up to temperatures of 165175 C.Moreover because of the fact that these polyvinyl resins do not havedefinite fusion points and do not become fluid at temperatures belowtheir decomposition temperatures, the unplasticized resins cannot beprocessed by wet-milling, extruding or molding, and particularly, thesematerials cannot be used for rotational casting techniques.

To overcome many of these difficulties it is common practice tointimately mix polyvinyl chloride resins with of article. In manyapplications it is desirable to use resin n compositions prepared byconventional formulation methods, which upon fusion and curing result inhard and rigid finished articles.

It is an object of this invention to provide improved halogen-containingvinyl resin compositions.

A further object is to provide novel plastic compositions comprisinghalogen-containing resins and certain low molecular weight, terminated,unsaturated polyesters.

A still further object of this invention is to provide new polymerizableplasticizers for vinyl chloride polymers and copolymers.

Another object is to provide new resin compositions which may be easilyprepared by conventional formulation methods and which, upon fusion andcuring, result in a hard, rigid material.

Further objects will be apparent to those skilled in the art from thefollowing description and claims.

In accordance with this invention it has been found that a resinouscomposition comprising a halogen-containing vinyl resin and, as apolymerizable plasticizer, a low molecular weight, terminated,unsaturated polyester of the type hereinafter described, may be fusedand cured to a hard and rigid material. The aforementionedcompositionsare prepared in a well known manner. -The resinous composition, uponmolding and curing, results in a hard and rigid material. p 7

Generally speaking, about 5 to 200 parts of plasticizer may be used foreach 100 parts of halogen-containing vinyl resin. However, it ispreferred to use from about 50 to parts of plasticizer per parts ofresin.

This invention is particularly applicable to polymerized vinyl chlorideresins andto resins formed by the conjoint polymerization of vinylchloride with other materials such as vinyl acetate, vinyl propionate,vinylidene chloride, methyl methacrylate or diethyl maleate, preferablywherein vinyl chloride comprises at least 70% of the copolymer resin.

In order to facilitate the curing of the polymerizable plasticizer inthe resin within a practicable time, it is preferred to incorporate fromabout 0.5% to 5% of a polymerization catalyst, based on the Weight ofthe Polymerizable plasticizer. While any of the usual peroxypolymerization catalysts such as benzoyl peroxide, acetyl peroxide,succinyl peroxide, methyl ethylketone peroxide, cumene hydroperoxide,t-butyl hydroperoxide, perbenzoic acid, peracetic acid and chlorinesubstituted aryl peroxides are eifective, it is preferred to use t-butylperbenzoate or benzoyl peroxide.

The usual heat stabilizers and light stabilizers for the resin may alsobe present in the resinous composition as indicated in theiexamplesbelow. Fillers and coloring materials well known to those familiar withthe art may also be added to the resin it desiredn The polymeri'zableplasticizers which are employed in the practice of this invention arelow molecular weight, terminated, unsaturated polyesters. Suchpolyesters comprise the residues of a dihydroxy aliphatic compound offrom 2 to 6 carbon atoms, a mono-olefinically unsaturated,aliphaticdicarboxylic acid of from 4 to 5 carbon atoms and a saturated,aliphatic dicarboxylic acidof from 4 to 10 carbon atoms, said polyesterbeing terminated with a residue selected from the residues ofmono-carboxylic saturated and unsaturated aliphatic acids of from 6 to20 carbon atoms, benzoic acid, naphthoic acid, saturated aliphaticalcohols of from 4 to 20 carbon atoms and phenylalkyl and phenoxyalkylalcohols of from 7 to 10 carbon atoms. The average molecular weight ofsuch polyesters is less than 4000. The ratio of saturated, dicarboxylicacid residue to unsaturated, dicarboxylic acid residue can vary from 1:3to 8:1.

As employed in this application, the phrase residue of a dicarboxylicacid designates the divalent radical which results from the removal ofthe hydroxyl group from each of the carbonyl carbon atoms. As employedin this application, the phrase residue of a dihydroxy aliphaticcompound designates the divalent radical which results from the removalof both of the hydroxyl hydrogen atoms. In each of these radicals Zrepresents Patented Sept. 15, 1964,

a divalent, aliphatic linking radical. As employed in thisapplicatiomthe phrase residue of a monocarboxylic acid designates themonovalent radical application, the phrase residue of an alcoholdesignates the monovalent radical Y' which results from the removal ofthe hydroxyl group.

The dihydroxy aliphatic compounds which are suitable for use ispreparing the polyester plasticizers of this invention include thealkylene glycols such as ethylene glycol, 1,2-propanediol,1,3-propanedil, 2-methyl-2-ethyl- 1,3-propanediol, 1,2-butanediol,l,3-butanediol, 1,4-butanediol, 2,3-butanediol,2,2-dirnethy1propane-1,3-dio1, l, 4-pentanediol, 1,6-hexanediol,2-methyl-2,4-pentanediol and the like, and the polyalkylene glycols suchas diethylene glycol, triethylene glycol anddipropylene glycol.

The mono-olefirn'cally unsaturated dicarboxylic acids which are suitablefor use in preparing the polyester plasticizers of this inventioninclude maleic acid, fumaric acid, itaconic acid and citraconic acid. Itwill be recognized that the corresponding anhydrides can also beemployed since the residues yielded are identical.

The saturated aliphatic dicarboxylic acids which are suitable for use inpreparing the polyester plasticizers of this invention include succinicacid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaicacid and sebacic acid.

The monocarboxylic acids which are suitable as termi nators for thepolyester plasticizers of this invention include the saturated acidssuch ascaproic, en ant-hic, caprylic, pelargonic, capric, und'ecanoic,lauric, myristic, palmitic, steari'c, arachidic and the like, theunsaturated acids such as decylenic, palmitoleic, oleic, linoleic andthe like, and the aromatic acids such as benzoic and naphthoic.

. The alcohols which are suitable as terminators for the polyesterplasticizers of this invention include the saturated aliphatics suchasn-butyl alcohol, t-butyl alcohol, isoamyl alcohol, neopentyl alcohol,n-hexyl alcohol, noct'yl alcohol, n-nonyl alcohol, lauryl alcohol,myristal alcohol, cetyl alcohol, n-eicosyl alcohol and the like; thephenylalkyl alcohols such as benzyl alcohol, phenylethyl alcohol,phenylbutyl alcohol and the like; and the phenoxyalkyl alcohols such asphenoxymethyl alcohol, phenoxybutyl alcohol and the like.

The low molecular weight, terminated, unsaturated polyester plasticizersof this invention are linear in nature. Said polyester can be furthercharacterized by the following general formula 1 wherein n, thetheoretical number of recurring units, has an average value of from 2 to20, each Xlis selected from the group consisting of saturated aliphatichydrocarbons of from 2 to 8 carbon atoms and mono-olefinicallyunsaturated aliphatic hydrocarbons of from 2 to 3 carbon atoms, theratio of saturated to. unsaturated hydrocarbons represented by X beingfrom 1:3 to 8:1, G is selected from the group consisting of alkylene andoxyalkylene of from 2 to 6 carbon atoms, R and R are each selected fromthe group consisting of alkyl and alkenyl of from to 19 carbon atoms,phenyl and na'phthyl, M is selected from alkyl of 4 to 20 carbons andphenylalkyl and phenoxyalkyl of from 7 to 10 carbon atoms, and x and yare unlike integers selected from 0 and 1. As employed herein, the termoxyalkylene designates the divalent ether group which forms the centralportion of a polyalkylene glycol such as CH -OCH in diethylene glycol.

Within the general formula given above, a particularly preferred groupof polyesters are those wherein n has an average value of from 6 to 16,each X is selected from (CH and CH=CH, the ratio of --(CH to -CH=CH- isfrom 1:2 to 3:1, G is alkylene of from 2 to 6 carbon atoms, and R and Rare alkyl of from 7 to 17 carbon atoms. Such preferred polyestersdisplay the most desirable properties and are most readily prepared inview of the availability of starting materials.

Thus it can be seen that the polymerizable plasticizers of thisinvention are linear polyesters having a chain wherein a mixture ofsaturated and unsaturated dicarboxylic acid residues are spaced byaliphatic glycol residues, such glycol residues being from a singleglycol or from a mixture of glycols. monocarboxylic acid residues whichterminate said'chain can be residues of a single acid or residues of amixture of acids.

The polyesters of this invention are prepared by charging a reactionvessel with an excess of glycol or glycols, a mixture of saturated andunsaturated dicarboxylic acids (within the ratio set forth above), aterminating mono-. carboxylic acid, acids or alcohol, and atransesterification EXAMPLE I In a 1 liter three-necked flask equippedwith a stirrer,

sub-surface carbon dioxide inlet tube, thermometer and a six inchpunched column with a condenser was charged 210 grams (2.34 moles) of1,3-butanediol, 73.05 grams (0.500 mole) of adipic acid, 58.0 grams(0.500 mole) of fumaric acid and 34.4 grams (0.200 mole) of capric acid.The mixture was flushed with a steam of carbon dioxide ('20 Ink/min.)for 15 minutes. Then four drops (0.0834 gram, 4.39 10- moles) oftitanium tetrachloride was added to the mixture, and heat was applied tothe flask. At 140-160" C. distillation of water began, and the carbondioxide How was regulated to maintain a vapor temperature below 106 C.The reaction temperature was increased to l90200 C. over a one hourperiod. After about 38 ml. of Water had been collected, the carbondioxide flow was removed and the system was placed under a vacuum ofabout 450 mm. maintaining the temperature at 195-200 C. After anadditional one-half hour, about 42 ml. of distillate had been collected,indicating that the esterification cycle was com plete. The distillatereceiver was changed,'and vacuum was slowly reduced to 3-4 mm. during anhour and a half period, while the reaction temperature was increased to2l0215 C. At about 300 mm., glycol started distilling from the batch.The vacuum was reduced slowly to prevent ester from distilling over withthe glycol. The 3-4 mm. of vacuum was maintained for one-half hour withthe reaction temperature at 215 C. Approximately 112 ml. of glycoldistillate was collected. The batch was allowed to cool to 125 C. andfiltered through filter aid.

' The yield of polyester was 219.8 grams.

Illustrative are the copolymers of a vinyl halidesuch as vinyl chloridewith such materials as vinylidene chloride, vinyl esters of carboxylicacids, e.g. vinyl acetate, vinyl propionate, vinyl butyrate, vinylbenzoate; estersof unsaturated acids, e.g. alkyl acrylates such asmethyl acrylate,

It can also be seen that the ethyl acrylate, propyl acrylate, butylacrylate, allyl acrylate, and the corresponding esters of methacrylicacid; vinyl aromatic compounds, eg styrene, ortho-chlorostyrene,para-chlorostyrene, 2,5-dichlorostyrene, 2,4-dichlorostyrene, para-ethylstyrene, vinyl naphthalene, a-methyl styrene; dienes such as butadiene,chlorobutadiene; unsaturated amides such as acrylic acid amide, acrylicacid anilide; unsaturated nitriles such as acrylic acid nitrile; estersof u,B-unsaturated carboxylic acids, e.g. the methyl, ethyl, propyl,butyl, amyl, hexyl, heptyl, octyl, allyl, methallyl and phenyl esters ofmaleic, crotonic, itaconic and fumaric acids and the like.

It should be recognized that the halogenated resins containing halogensother than chlorine, e.g. bromine, fluorine and iodine, are alsooperable in this invention. Said halogenated resins may contain avarying proportion of halogen depending upon the nature of the resin andits contemplated use. Those copolymers in which a predominant portion,i.e., more than 50% by weight of the copolymer is made from ahalogen-containing vinyl compound such as vinyl chloride represents apreferred class of polymers to be treated according to this invention.

The polymerizable plasticizers ofthis invention are not only compatiblewith the various vinyl resins described above but are also compatiblewith the known non-polymerizable ester plasticizers commonly employedwith such resins. Illustrative of these latter plasticizers are thealkyl and aryl phosphates, the alkyl phthalates, adipates, sebacates andazelates, and the epoxidized vegetable oils. Specific examples of suchknown plasticizers include tri- (Z-ethylhexyl)phosphate, tricresylphosphate, di-(Z-ethresinous compositions. Such monomeric cross linkingagents include vinyl compounds such as vinyl benzoate', vinyl crotonate,cyanovinyl acetate, vinyl toluene, divinyl toluene, bis(fi-chloroethyDvinyl phosphonate, butyl vinyl ether, and the like, andpolyallyl esters such as diallyl adipate, triallyl citrate, diallylphthalate, diallyl sebacate,- and the like.

Excellent resinous compositions have been made by in: timately mixing ahalogen-containing vinyl resin with a; mixture of a polyesterplasticizer and one ofthe nonpolyrnerizable plasticizers describedabove. The ratio of polyester to non-polymerizable plasticizer will varyover a wide range depending upon the type of resin and the finalproperties desired. A major proportion of either plasticizer can beemployed.

Resinous compositions have also been prepared with the polyesterplasticizers and the monomeric vinyl and polyallyl cross linking agents.In such compositions the ratio of polyester to agent should be at leastabout 3:2. It is particularly preferred to employ at least a 2:1 ratioof polyester to cross linking agent.

The invention will be more fully understood by refer ence to the severaltables hereinafter presented. However, the preparations set forth insuch tables are illustrative only and are not to be construed aslimiting the scope of the present invention in any manner.

Table I lists a number of polyesters prepared in accordance with theprocedures detailed in Example I. The specific reactants, the averagenumber of recurring units (n in the formula above) and the ratios ofreactants, where appropriate, are given.

Table I Diearboxylic acids Average,

- number Polyester Glycol Terminating acid (s) or recur- SaturatedUnsatu- Ratio of v ring units rated s:u

1,2-propylene Ma1eic 5. 7:1 Stearic and oleic 13 do do. 5. 7:1 Palruiticand oleic 13 do 3:1 Oapric. 8 Fumaric 3 :1 8 aleic 2:1 6 Fumarie 2 :1 6Maleic- 2 1 10 Fumarim 2:1 10 Maleic 2:1 14 Fumaric 2:1 14 lVl'nlPio1.221 10 do 3:1 10 Fumaric- 3 :1 10 (1 2:1 10 3:1 10 5:1 12 1:1 6 1:1 101:2 6 1:2 10 2:1 6 3:1 10 2. 5:1 10 1:1 10

1 Ratio of stearie to o1elc2:1. 2 Ratio of palmitic to oleicl:

ylhexyl)phthalate and the corresponding adipate, dioctyl sebacate, andepoxidized soy bean oils.

The polymerizable plasticizers of this invention are also compatiblewith various unsaturated monomeric compounds which are employed as crosslinking agents in Resinous compositions were prepared from ahalogencontaining vinyl resin and several of the polyesters in Table 1.Such compositions are set forth in Table II, all parts being parts byweight. Other components employed in said compositions are alsoindicated.

Table II Polyvinyloh10ride.100 100 100 100 100 100 100 100 100 100 100100 100 100 100 100 100 100 100 100 100 100 100 100 PolyesterL 50 75 5075 50 75 50 75 Polyester M. 50 75 50 75 50 75 50 75 Polyester S.PolyesterT Polyester R Polyester Q Polyester U Polyester H Polyester 0zoate .25 .25 .25 .25 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 Benzoylperoxide. .25 .25 .25 .25 .5 .5 .5 .5 Leadstearate .5 .5 .5 .5 .5 .5 .5.5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 .5 BisphenolA .25 .25.25 .25 .25 .25 .25 .25

Table III Kero- Humid- Several of the resinous compositions set forth inTable Com osition No. Hard- Volasens ity eorn- Tensile II were pressuremolded for 3 minutes at 325 F. The I mess ig? x3 Strength finishedproducts were then tested for various physical 7 properties. a The testprocedures are hereinafter described, 1 45 3 85 2 2,973 and the resultsobtained are hsted m Table III. g; 1 .33 3&3

Hardness--A Shore Durorneter Hardness Tester was I 31 2 2:786 employed,and the D scale was used. The specimen g V 8. 3 tested was of 80 milsthickness, and the spring loaded 64 1 1 10 s eonds. 34 1.1 0.57 1

penetrator was held down for e g2 1 i Volatility -A.S.T.M. D-1203-55 j45 :1 1 1.1 0. 59 2 Kerosene extraction A.S.T.M. D 1239 55 3% 1 2?Hum-idityCompatibility--This was determined on the j 48 j 58 1 basis ofthe amount of exudation which occurred after g? 3-33 aging in a watervapor saturated atmosphere for two weeks I 78 8 1 at 60 C. Values areemployed from 1 to 4 1n order of 83; increasing exudation. 73 0.9 0. 5s1 a 3-5 1 Tensile strength -A.S.T.M. D-882-56T 24 50 1 III: 7

except that the dumbell was of mils thickness and measured 50 mils by500 mils. The rate of loading was 2 Results similar to those detailedabove are obtained inches per minute. Break p.s.i. was recorded, Whenother and different low-molecular weight, terminated, unsaturatedpolyesters of this invention are employed in preparing the resinouscompositions. Such other and different polyesters include the following:

Table I V Dicarboxylie acids Average Glycol Terminating acid(s) numberof recur- Saturated Unsaturated Ratio oiszu ing units DiethyleneSueeinie. Fumarie 2:1 Myristie 1o Itac0nic 1: 2 12 Ethylene Citraeonic.3: 1 10 1,4- entanediol Fumaric. 1: 1 6 2,2-dimethypropane-1,3-diol. Mal2;1 4 1 ,fi-hoxanediol Fumarie. 2:1 1 2-methyli-2A pentanedi masonic.--2: 1 14 1 ,3-butylene Citraeonic- 1:1 2 1,2-propylene I M aleie 1: 1 101,3-butylene. Glutarie. Fumaric. 2: 1 1 Dipropylene.-. Adipic Maleie 3:14 1,3-butylene. Suecinie. Ita0onic.--- 3 :1 g Diethylene. d Fumaric. 2:112 Dipropyleue. Its/conic--- 1: 2 6 Ethylene Oitraconic. 3: 1 41,4-pentanediol. Fumarie. 1: 1 14 2,2-dimethylpropane-3,3-diol Meleic2:1 16 1,6-h exanediol Fumarie 2:1 10 2-metl1yl-2A-pentanediolBecome".-- 2: 1 '10 1,3-butylene Citraeonic. 1 :1 10 1,2-propy1ene-Maieie 1:1 1,3-butylene.-. Fumarlc. 2:1 1 Dipropylene Adipie Maleic-.- S1 1,3-butylene Succinie. Itaeonic 3:1 PhenoxybutyL 1 Ratio of stearie toeaprio-kl. I

IRCXIION 9 Numerous resinous compositions comprising a halogencontainingvinyl resin, a polymerizable polyester plasticizer, and either or both anon-polymerizable plasticizer and a cross linking agent were prepared.The components 10 G is selected from the group consisting of alkyleneand oxyalkylene of from 2 to 6 carbon atoms; R and R are each selectedfrom the group consisting of alkyl and alkenyl of from 5 to 19 carbonatoms,

of such compositions are set forth in Table V. 5 phenyl and naphthyl;

Table V Composition N0. (parts by weight) Components 25 26 27 2s 29 3031 32 33 34 35 as 37 3s 39 40 41 42 Polyvinyl chloride 100 100 100 100100 100 100 100 100 100 100 100 100 100 100 100 100 100 PolyesterA 35 lPolyester D 40 40 20 20 50 50 70 70 70 70 60 e 60 60 60 60 60 Vinyltolnene l0 l0 Diallyl phthala Triallyl citrate tDi-(2ethylhexyl)phthalate 60 50 Diallyl sebacate 30 30 Divinyl t0luene10 10 Vinyl benzoate t-" 20 Bis(B-chloroethyl)v1nyl phosphonate 20Diallyl adipate 20 l cyanovinyl acetate" t..- 20 Vinyl crotonate 20n-Butyl vinylether 20 t-Butyl perbenzoate .5 1 1.5 t .2 1 Benzoylperoxide .5

While this invention has been described with respect to M is selectedfrom alkyl of from 4 to 20 carbon atoms, certain embodiments, it is notso limited and it is to be and phenylalkyl and phenoxyalkyl of from 7 to10 understood that variations and modifications thereof may carbonatoms; and be made without departing from the spirit or scope of this xand y are unlike integers selected from 0 and 1. invention. 4. Acomposition as defined in claim 3 wherein the The embodiments of theinvention in which an eX- polyester is present in amounts of from 5to200 parts by clusive property or privilege is claimed are defined asWeight per 100 parts by weight of vinyl halide polymer. follows; v 5. Acomposition of matter comprising a vinyl chloride 1. A composition ofmatter comprisinga vinyl halide polymer selected from the groupconsisting of polymerized polymer selected from the group consisting ofpolymerized vinyl chloride monomers and the copolymers of such vinylhalide monomers and the copolymers of such monomers with anethylenically unsaturated monomer, at monomers with an ethylenicallyunsaturated monomer, at least 50% of the monomer units of saidcopolymers being least 50% of the monomer units of said copolymers beingvinyl chloride units, and a terminated, unsaturated polyvinyl halideunits, and a terminated, unsaturated polyester ester consistingessentially of the residues of a dihydroxy consisting essentially of theresidues of a dihydroxy alialiphatic compound of from 2 to 6 carbonatoms, a' phatic compound of from 2 to 6 carbon atoms, amonomonoolefinically unsaturated, aliphatic dicarboxylic acidolefinically unsaturated, aliphatic dicarboxylic acid of of from 4 to 5carbon atoms, and a saturated, aliphatic difrom 4 to 5 carbon atoms, anda saturated, aliphatic dicarboxylic acid of from 4 to 10 carbon atoms,said poly-v carboxylic acid of from 4 to 10 carbon atoms, said poly- 45ester being terminated with a residue selected from the ester beingterminated with a residue selected from the group c nsisting of theresidues of monocarboxylic group consisting of the, residue ofmonpcarboxylic saturated and unsaturated aliphatic acids Of from 6 t0saturated and unsaturated aliphatic acids of from 6 to 20 2Q carbonatoms, benzoic acid, naphthoic acid, saturated carbon atoms, benzoicacid, naphthoic acid, saturated ip i 3116011018 of from t0 20 Carbonatoms and aliphatic alcohols of from 4 to 20 carbon atoms andphenylalkyl and phenoxyalkyl alcohols of from 7 to 10 phenylalkyl andphenoxyalkyl alcohols of from 7 to 10 carbon atoms, the rat1o ofsaturated to unsaturated dicarbon atoms, the ratio of saturated tounsaturated dir oxyhc aCld residu s being from 1:3 to 8:1. carboxylicacid residues being from 1:3 to 8:1. 6. A compositlon as defined inclaim 5 wherein the 2. A composition as defined in claim 1 wherein thePolyester 18 Present in amc'unts of from 5 to 200 P polyester is presentin amounts of from 5 to 200 parts by y Weight P61 100 PaIts y Weight ofvinyl Chloride weight per 100 parts by weight of vinyl halide polymer. Py g 3. A composition of matter comprising a vinyl halide A COQPOSIUOIIdefined 111 claim 5 wherein the polymer selected from the groupconsisting of polymerized y chloride polymer is polyvinyl Chloride.vinyl halide monomers and the copolymers of such A p o f a r pri v y lri monomers with an ethylenically unsaturated monomer, at Pf y le fromthe group consisting of polymerized least 50% of the monomer units ofsaid copolymers being vlflyl Chlofld? m0110I116r$ and copolymers of Suchvinyl halide units, and a terminated, unsaturated polyester monomersWith an ethylemcallv unsaturated monomer, at of h f r ul least 5 0% ofthe monomer units of said copolymers being vinyl chloride units, and aterminated, unsaturated poly- E) (H) E 65 ester of the formula I R (M)OG[OCX OG]L10( )YOR! g 0 wherein: R-O x(M y-o-o[0oX-ii0-G]..o- M),(ii-R)x n is an integer from 2 to 20;

each X is selected from the group consisting of saturated whefemialiphatic hydrocarbons of from 2 to 8 carbon atoms 15 an f from 2 t0 andmono-olefinically unsaturated aliphatic hydroeach X ls.selectad fromgroup conslstlng of Satucarbons of from 4 to 5 carbon atoms, the ratioof rated aliphatic hydrocarbons of from 2 t0 8 carbon saturated tounsaturated hydrocarbons represented atoms and mono-olefinicallyunsaturated aliphatic byXbeingfrom1:3to 8:1;

hydrocarbons of from 4 to 5 carbon atoms, the ratio l 1 of saturated tounsaturated hydrocarbons represented by X being from 1:3 to 8:1;

G is selected from the group consisting of alkyle-ne and oxyalkylene offrom 2 to 6 carbon atoms;

R and R are each selected from the group consisting of alkyl and alkenylof from 5 to 19 carbon atoms, phenyl and naphthyl;

M is selected from alkyl of from 4 to 20 carbon atoms, and phenylalkyland phenoxyalkyl of from 7 to 10 carbon atoms; and

x and y are unlike integers selected from and 1;

9. A composition as defined in claim 8 wherein the polyester is presentin amounts of from 5 to 200 parts by weight per 100 parts by weight ofvinyl chloride polymer.

10. A composition as defined in claim 8 wherein the vinyl chloridepolymer is polyvinyl chloride.

11. A composition of matter comprising a vinyl halide polymer selectedfrom the group consisting of polymerized vinyl halide monomers and thecopolymers and the copolymers of such monomers with an ethylenicallyunsaturated monomer, at least 50% of the monomer units of saidcopolymers being vinyl halide units, and a terminated, unsaturatedpolyester of the formula v n is an integer from 6 to 16;

each X is selected from -(CH and CH=CH, the ratio of -(CH to -CH=CH isfrom 1:2 to 3: 1;

G is alkylene of from 2 to 6 carbon atoms; and

R and R are alkyl of from 7 to 17 carbon atoms.

12. A composition as defined in claim 11 wherein the polyester ispresent in amounts of from 5 to 200 parts by weight per 100 parts byweight of vinyl chloride polymer.

13. A composition of matter comprising a vinyl chloride polymer selectedfrom the group consisting of polym erized vinyl chloride monomers andthe copolymers of such monomers with an ethylenically unsaturatedmonomer, at least 50% of the monomer units of said copolymers beingvinyl chloride units, and a terminated, un-

wherein:

n is an integer from 6 to 16;

each X is selected from (CH and CH=CH,

the ratio of (CH to CH=CH is from 1:2 to 3:1;

G is alkylene of from 2 to 6 carbon atoms; and

R and R are alkyl of from 7 to 17 carbon atoms.

14. A composition as defined in claim 13 wherein the polyester ispresent in amounts of from 5 to 200 parts by weight per 100 parts byweight of vinyl chloride polymer.

15. A composition as defined in claim 13 wherein the vinyl chloridepolymer is polyvinyl chloride.

16. A composition of matter comprising polyvinyl chloride and aterminated, unsaturated polyester consisting essentially of the residuesof an alkylene glycol of from 2 to 6 carbon atoms, adipic acid andfurnaric acid, said polyester being terminated with the residue of asaturated, aliphatic, monocarhoxylic acid of from 8 to 18 carbon atoms,the ratio of adipic acid residues to fumaric acid residues'being from1:2 to 3:1, said polyester being present in amounts of from 5 to 200parts by Weight per 100 parts by weight of polyvinyl chloride.

17. A composition of'matter comprising a vinyl halide polymer selectedfrom the group consisting of polymerized vinyl halide monomers and thecopolymers of such monomers with an ethylenically unsaturated mon- 1'2omer, at least 50% of the monomer units of said copolymers being vinylhalide units, a terminated, unsaturated polyester of the formula a t 0 011-23 =(M) -oG[-o-tiX U -OG]nO(l\1)y R' x wherein:

n is an integer from 2 to 20;

each X is selected from the group consisting of saturated aliphatichydrocarbons of from 2 to 8 carbon atoms and mono-olefinicallyunsaturated aliphatic hydrocarbons from 4 to 5 carbon atoms, the ratioof saturated to unsaturated hydrocarbons represented by X being from 1:3to 8: 1;

G is selected from the group consisting of alkylene and oxyalkylene offrom-2 to 6 carbon atoms;

Rand R are each selected from the group consisting of alkyl and alkenylof from 5 to 19 carbon atoms, phenyl and naphthyl;

M is selected from alkyl of from 4 to 20 carbon atom and phenylalkyl andphenoxyalkyl of from 7 to 10 carbon atoms; and

x and y are unlike integers selected from 0 and 1; and

an ester selected from the group consisting of alkyl and arylphosphates, alkyl phthalates, alkyl adipates, allryl sebacates, alkylazelates and epoxidized vegetable oils, the combined amount of polyesterand ester being from 5 to 200 parts by weight per parts by weight ofvinyl halide polymer.

18. A composition as defined in claim 17 wherein the ester is an alkylphthalate.

19. A composition as defined in claim 18 wherein the vinyl halidepolymer is a vinyl chloride polymer.

20. A composition as defined in claim 19 wherein the alkyl phthalate isdi-(Z-ethylhexyl)phthalate.

21. A composition of matter comprising a vinyl halide polymer selectedfrom the group consisting of polymerized vinyl halide monomers and thecopolymers of such monomers with an ethylenically unsaturated monomer,at least 50% of the monomer units of said copolymers being vinyl halideunits, a terminated, unsaturated polyester of the formula n is aninteger from 2 to 20;

each X is selected from the group consisting of satu rated aliphatichydrocarbons of from 2 to 8 carbon atoms and mono-olefinicallyunsaturated aliphatic hydrocarbons of from 4 to 5 carbon atoms, theratio of saturated to unsaturated hydrocarbons represented by X beingfrom 1:3 to 8:1;

G is selected from the group consisting of alkylene and oxyalkylene offrom 2 to 6 carbon atoms;

R and R are each selected from the group consisting of alkyl and alkenylof from 5 to 19 carbon atoms, phenyl and naphthyl;

M is selected from alkyl of from 4 to 20 carbon atoms, and phenylalkyland phenoxyalkyl of from 7 to 10 carbon atoms; and

x and y are unlike integers selected from 0 and 1; and

a compound selected from the group consisting of vinyl and polyallylesters, the ratio of polyesters to compound being at least 2:1.

22. A' composition as defined in claim 21, the combined amount ofpolyester and compound being from 5 to 200 parts by weight per 100 partsby weight of vinyl halide polymer.

23. A composition as defined in claim 22 wherein the compound is apolyallyl ester.

24. A composition as defined in claim 23 wherein the vinyl halidepolymer is polyvinyl chloride.

25. A composition as defined in claim 24 wherein the polyallyl ester isdiallyl adipate.

26. A composition as defined in claim 24 wherein the polyallyl ester isdiallyl phthalate.

27. A composition of matter comprising a vinyl halide polymer selectedfrom the group consisting of polymerized vinyl halide monomers and thecopolymers of such monomers with an ethylenically unsaturated monomer,at least 50% of the monomer units of said copolymers being vinyl halideunits, a terminated, unsaturated polyester of the formula n is aninteger from 2 to 20;

each X is selected from the group consisting of saturated aliphatichydrocarbons of from 2 to 8 carbon atoms and mono-olefinicallyunsaturated aliphatic hydrocarbons of from 4 to 5 carbon atoms, theratio of saturated to unsaturated hydrocarbons represented by X beingfrom 1:3 to 8:1;

G is selected from the group consisting of alkylene and oxyalkylene offrom 2 to 6 carbon atoms;

R and R are each selected from the group consisting of alkyl and alkenylof from 5 to 19 carbon atoms, phenyl and naphthyl;

M is selected from alkyl of from 4 to 20 carbon atoms, and phenylalkyland phenoxyalkyl of from 7 to 10 carbon atoms; and

x and y are unlike integers selected from 0 and 1; and

an ester selected from the group consisting of alkyl and arylphosphates, alkyl phthalates, alkyl adipates, alkyl sebacates, alkylazelates and epoxidized vegetable oils, and a compound selected from thegroup consisting of vinyl and polyallyl esters, the ratio of thepolyester to the compound being at least 2:1, and the combined amount ofpolyester, ester and comsuch monomers with an ethylenically unsaturatedmonomer, at least of the monomer units of said copolymers being vinylchloride unlts, a terminated, unsaturated polyester of the formula O OR( 3OG[O iX O-G]n-O R wherein:

n is an integer from 6 to 16; each X is selected from (CH and CH=CH, theratio of --(CH to CH:CH is from 1:2 to 3:1; G is alkylene of from 2 to 6carbon atoms; and R and R are alkyl of from 7 to 17 carbon atoms; and anester selected from the group consisting of alkyl and aryl phosphates,alkyl phthalates, alkyl adipates, alkyl sebacates, alkyl azelates andepoxidized vegetable oils, the combined amount of polyester and esterbeing from 5 to 200 parts by weight per parts by weight of vinyl halidepolymer 30. A composition as defined in claim 29 wherein said ester isdi-(2-ethylhexyl)phtl1alate.

References Cited in the file of this patent UNITED STATES PATENTS

3. A COMPOSITION OF MATTER COMPRISING A VINYL HALIDE POLYMER SELECTEDFROM THE GROUP CONSISTING OF POLYMERIZED VINYL HALIDE MONOMERS AND THECOPOLYMERS OF SUCH MONOMERS WITH AN ETHYLENICALLY UNSATURATED MONOMER,AT LEAST 50% OF THE MONOMER UNITS OF SAID COPOLYMERS BEING VINYL HALIDEUNITS, AND A TERMINATED, UNSATURATED POLYESTER OF THE FORMULA
 27. ACOMPOSITION OF MATTER COMPRISING A VINYL HALIDE POLYMER SELECTED FROMTHE GROUP CONSISTING OF POLYMERIZED VINYL HALIDE MONOMERS AND THECOPOLYMERS OF SUCH MONOMERS WITH AN ETHYLENICALLY UNSATURATED MONOMERS,AT LEAST 50% OF THE MONOMER UNITS OF SAID COPOLYMERS BEING VINYL HALIDEUNITS, A TERMINATED, UNSATURATED POLYESTER OF THE FORMULA